Cellulose-ester composition



- Patented Jul 10, 1928.

' UNITED ST TES" PATENT" OFFICE.

IBICHABD L. KRAMER, or wr memon; DELAWARE, AssIGNoa To It I. no 201w Dnnuouns a conrm, or WA E- v .cELLULosE-Es'rER COMPOSITION.-

lium-swing.

' This inventionrelates to cellulose ester, particularly cellulosenitrate, compositions containing a softener, and has particular relationto the manufacture of artificial leather of which films or layers ofpyroxylin constitute an essential part. By softener I of course mean amaterial impartin ,flexi bility to the film'and of such low vo atilitythat said material will remain fora long riod as a constituent of thepyroxylin coatmg or film of which itioriginally'formed a part. Of thesofteners heretofore used 03S?- tor oil is a typical example. .Adifiiculty with it is that it is subject to oxidation and.

- can be'used for coating .woven fabrics to.

- produce artificial leather or fabrikoidhavgreat durabilityandpliability and with a Im not liable. to the various faults, asrancidity development, coldcracking and so on,-

A further. object is to.

' -of previous films. I

provide an artificial leather having the desirable characteristicsmentioned. To these ends, and also to improve generally uponcompositions, coatings, and artificial leathers, the invention consistsin the following matters hereinafter described and claimed." 1 havefound-that aryloxyf-ethanol esters of carboxylic acids are highlysatisfactory softeners, having excellent softening propera'nd'wearingqualities. Of the various esters particular mention is made ofbeta-phenoxyethyl phthalate, beta-'methyl-phenoxy-ethyl phthalate, andbeta-methyl-phenoxyethyl' 40 laurate. As a specific example illustratingmy 111-- as; above,- whilein using betamethyl-phe- Y noxy-ethyl lauratethe range may be .7 5-220. Thepigment may be any-of the usual p1gments,as zinc oxide forgwhite goods. The

.ties, not exuding from the film during em-" 35 bossing, and givingfilms of proper pllabllity WILMINCgTON, DELAWARE, A CORPQRATION OF DELA-Application'filed September 6, 1924. Serial .No. 736,367.

solvent may. be any suitable one as 95% ethyl alcohol.5 0, ethyl acetate50. As will be understood, the. proportions of pigment and solvent maybe varied as desired to meet particular conditions and as wellunderstood in .theart. The composition may be.

applled to the goods,'in the production of artificial leather, inaccordance with the general practices of the art, the present softenersintroducing no, complications into coating practices. 1 J The substancesspecifically mentioned above may be prepared as follows Beta-phenomethyl pkthaZate.Heat together in a flask 100 grams of beta-phenoxyethanol (Bentley, Haworth and Perkin, J. Chem. Soc, 69, (1896) 164) and54 grams-of phthahc anhyd'ride, on a steam bath for 4 hours. Pass HClgas through for 15 min-- 'utes. Again heat on steam bath for 2 hours;

pass HCI gas through for 15 minutes; transfer flask to oil bath and heatat 115120 C. I

for 4 hours. Transfer flask to steambath and heat'continuously for 2days to drive off the last traces of hydrogen chloride.

)Vash produ ct Wit l1 water and then with sodium carbonate solutionuntil neutralized. Again wash twice with water, and separate. Thecompound is a'solid substance at 20 C.

Bcta-methylphenowy ethyl plttlialwter- Heat together in a flask 100grams of betam'ethyl-phenoxy ethanol (Boyd and Marle,

J. Chem. Soc., 105, (1914) 2133), ortho-or meta beingsatisfactory, or amixture of para with the others, the solid para" being soluble in theothers, and 49 grams of phthalic anhydride for 4 hours on a steam bath.Pass HCl gas through for 15 minutes. Again heat onsteam bath for 2hours;pass HC'l gas through for 15"minutes; transfer flask to oil bathandhea't at 115120 C. for 4 hours. Transfer to steam bath and heatcontinuously for 2 day'sto drive off last'traces of hydrogen chloride.Wash product with water and then with sodium carbonate solution untilneutralized. Again wash twlce with water, andsep'arate. The compound isa viscous liquidat 20 C. With a slight but pleasant odor.' g

Beta-wwtkyZ-phenowy-ethyl Zaumta+Heat together in a flask 20 grams ofbeta-methylplienoxy ethanol and 27 grams coconut oil acidsv by oil bath.When temperature of bath reaches 127 C; start a stream of. nitrogenbubbling through the mixture to sweep out Water of estrification andcontinue the heating under these conditions until the product is almostneutral, Wash with salt water, filter, and, if desired, decolorize withany suitable agent as decoloriz'ing charcoal.

The'compound is a liquid which begins to freeze at about 1. C. and has aviscosity about equivalent to that of liquid coconut be understood thatit is to the dior neutral phthalates that particular reference is made.

It will be understood that other aryloxyethanol esters of carboxylicacids may be used in place of those; esters previously mentioned.Compounds having an aryl nucleus with a hydroxyl group united directlywith a carbon of the nucleus are, in general, suitable for use inpreparing the desired esters. Na'phthol C H OH and its derivatives asWell as the various phenoxy derivatives in which a hydrogen of the arylring has been replaced by a substitue'nt atom or radical, are suitable.As a specific example, beta methyl naphthoxyethanol, I a

may be used in place of the other softeners.

It will be understood that many changes and variations may-be made inthe invention without departing from the scope thereof.

I claim 1. A product comrising cellulose nitrate and as a softenertherefor a carboxylic acid ester of an aryloxy ethanol.

. 2. A product comprising cellulose' nitrate I phthalate.

and as a softener therefor'a phthalic acid ester of an a-ryloxy ethanol.

3.1A product comprising cellulose nitrate and. as a softener therefor aplienoxy-ethyl 4. A product comprising cellulose nitrate and as asoftener therefor methyl-phenoXyethyl phthalate. a 5. Aproductcomprising cellulose nitrate and methyl-phenoxy-ethyl phthalatein Substantially the proportion of .75 to 2.0 parts of phthalate to 1 ofpyroxylin.

6. A product comprising cellulose nitrate and methyl-phenoxy-ethylphthalate 1n substantially the proportion of 1.37 parts of phthalate to.1 of pyroxylin.

7, A liquid coating composition comprising cellulose-nitrate, volatilesolvent therefor and as a softener for t 1e nitrate a carboxylic acidester of a phenoxy ethanol.

8. A liquid coating composition comprising cellulose nitrate,volatilezsolvent therefor, and a phenoXy-ethyl phthalate.

9. A liquid coating composition comprising cellulose nitrate, volatilesolvent the-refor,-and methyl-phenoxy-ethyl phthalate.

'10. An artificial leather comprising a fabric base having a filmcomprising cellulose nitrate and a carboxylic acid ester of a phenoxyethanol as a softener for. said film.

11. An artificial leather comprising a fabric base having a filmcomprising cellulose nitrate and a phenoxy-ethylphthalate as. a softenerfor the film. 2

ric base having a film comprising cellulose nitrate andmethyl-phenoxy-ethyl phthalate .as a. softener for the film. 1

13. .An artificial leather comprising a fab: ricbase having a filmcomprising cellulose nitrate and a carboxylic acid ester of an aryloxyethanol as a. softener for said film.

ing cellulose nitrate, volatile solvent therefor, and as. a softener forthe nitrate a carboxylic acid ester of an aryloxy ethanoh 12.Anartificial leather comprisinga fab- 14. A liquid coat-ing compositioncom'prisa In testimony whereof I aflix my signature.

RICHARD L. KRAMER.

